Nature of the metal–ligand bond in some [(CO)4M ← BIIM(R)] {M = Cr, Mo, W; R = H, F, Cl, Br} complexes: A theoretical study. (28th May 2016)

• Record Type: Journal Article
• Authors: Bayat, Mehdi; Hatami, Masoud
• Is Part Of: Polyhedron. Volume 110(2016)
• Page Start: 46
• Page End: 54
• Publication Date: 2016-05-28
• Subjects: Metal–ligand bond -- DFT -- Orbital interaction -- EDA -- ETS-NOCV; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2016.02.022
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A theoretical study on the structure and nature of M ← N bonds in some potential pharmacologically active [(CO)4 M ← BIIM(R)] {M = Cr, Mo, W; R = H, F, Cl, Br} complexes have been investigated with the BP86 and MP2 methods using the def2-TZVPP basis set. Abstract: A theoretical study on the structure and nature of the M ← N bond in some potential pharmacologically active complexes; [(CO)4 M ← BIIM(R)] {M = Cr, Mo and W, R = H, F, Cl and Br} with R(3, 3 substitution), R(4, 4 substitution), R(5, 5 substitution) and R(3, 3 4, 4, 5, 5 substitutions) was carried through density functional BP86 and ab initio MP2 methods using the def2-TZVPP basis set. The M ← N bond was analyzed using NBO, AIM, EDA and ETS-NOCV to obtain the electrical charge and energy decomposition analysis (EDA). The results showed that [(CO)4 W ← BIIM(H)] and [(CO)4 Cr ← BIIM(F)] are related to the D form complex with the biggest and the smallest Δ E int, respectively. Additionally, the M ← N bond interaction energies (Δ E int ) increase in the group from top to bottom, from the lighter to the heavier elements (Cr < Mo < W). The EDA suggests that the [(CO)4 M ← BIIM(R)] attractive interactions come mainly from Δ E elstat, which provides ∼60% of Δ E int, while ∼40% comes from Δ E orb . The applicability of the ETS-NOCV scheme is demonstrated for the complexes and it is shown that the Δ E orb term arises mainly through [(CO)4 M ← BIIM(R)] σ-donation (in the range 54–61%) while a smaller part (∼27%) comes from [(CO)4 M → BIIM(R)] π-back donation. The nature of the M ← N bond in the complexes was also studied by AIM and NBO analyses. The data has confirmed that the M ← N bond is partly covalent.